Dyestuff of the anthraquinoneacridone series



Patented Sept. 4, 1934 "PATENT OFFICE Q;

s r r 1,972,095.

I D YES TUF I F OF, THE" ANTHRAQUINONE- j ACBI1DONE SERIES Ivan Gubelmann and Robert J. Goodrich, .South v Milwaukee, and William Dettwyler, Milwaukee, Wis., assignorsto E. I. du Pont de Nemours &

Company, Wilmington, D el., a corporation of czin aw Drawing.

a-anthraguinone diacridone zen). whelelll -oaa. refertothe positions of the NH smiles ?er 9ri gs es a residue of the anthraquinone series, :r stands for 1 or 2, .while zastands for a number not less than 4. The more important representatives of these have thezfollowihg general formula;:

wherein R.,.-i's-a residue ;of the anthraquinone :series, which may contain additional chromophoric group's"such as the benz'oyl amino group, while *,f= indicate the positions of. attachment-of the CO group'sfand-fwhich "may ben'ained' generically gen 02 anthraquinene diacriddnesi These novel intermediates may be prepared, forinanthraquinone series, and in'the presence of a -copper* salt and an acid binding agent, a polyhalogen 1,2,5,6- or 1,2,8,7-anthraquin0ne-'di 'ngi-idpn jcr .1 i' I q -We have-now found that these novel halogenated anthraquinonyl imino anthraquinoner- -ac 1'iddne oompoundsfialthough--valuable dyestuffs in themselves, may beifurther'condensed to give -i -tlirimidex-'acr idone-= eompeunde ar *heated with -More iparticularly; wefound "that when said an Application November 16, 1931,- 7 Serial N0. 575,478 13 Claims. (Cl. 260-37) metallic halides such as aluminum chloride, zinc chloride, ferric chloride and the like; the said compounds are convertedinto novel and very valuable dyestuffs of generally brown shades. In this reaction evidently a ring isformed about and involving the imide ('-NH-) group; however, it is not conclusive whether the product is an acridine V or a carbazole compound. In analogous reactions in the'art involving the heating of an anthrimide with ametallic chloride, the authorities seem to disagree sharply as to the nature ofthe ring formed. Some believe '7 that the ring is of an'acridine nature, involving the N atom from the imide group, and the adjacent meso C atom of one of the anthraquinone nuclei.

Other authorities, however, insist that the ring is of a carbazole nature involving the N atom of the imide group, and the adjacent beta C atom of the anthraquinonenucleus. In view of this uncertainty as to the precise nature of the ring formed, we shall hereinafter refer to our condensation products merely as ring-closed condensation products of the respective halogenated anthraquinonyl-imino-anthraquinonediacridones. I 5

Without limiting our invention to any particular procedure, the following examples are given to illustrate our preferred mode of operation.

Parts given are parts by weight.

" Example 1-" i 40 parts of aluminum chloride (anhydrous) and 60 parts of sodium chloride are melted together and heated to about 170 C., and into this 'melt are introduced 10 parts of .Bz,Bz-tetrachloro-4,5 -'di a e anthraquinonylamino 1,2,8,7-

anthraquinone-diacridone. (Example 1 of copending application Serial No. 575,477. The ,95

formula of the initial material is most probably:

and it may be prepared by reacting hexachloro- 1,2,8,7 anthraquinone diacridone *with Jae-aminoanthraquinone in the presenc'e of-sodium carbonate and cuprous chloride.) in temperature to about 180 C., and held at this temperature for about 1 hour. The melt is nowti pouredinto 1000 parts of hotwater, stirred lwella l filtered, washed with hot wateriuntirfree ofiacid; and dried. p The product is a black powder, in'solu ble in water, dilute acidfor dilute 381K811. I, It-tispractically insoluble in hot-nitrobenzene or dichloro-benzene. It is soluble "in concentrated sulfuric acid with a reddish bordeaux color,and is precipitated therefrom upon dilution with water in khaki colored flocks.

is dyed a blackish color, changing to khaki upon treatment with the usual oxidizing agents.

In the above example the fusedmi-xture of alulfchloride and sodium chloride may bere- Iplaced by other metallic chlorides with equally successful results. For instance, 50 parts of zinc chloride may be used, its. fusion temperature being lowered by. addition of a small amount of'water.

Example 2.

' The procedure [is] the sameas' inExziinple "1,

except that in lieu ofthe' halogenated-trianthriitetrachloro-4,5-di-( 5 benzoylamino 1 1- anthra- 'lquinonylaminol-1,23,! -,.anthraquino'ne -.,diac ridone are used. (Example 4 of. copending application SerialQNoI575A'77. The formula of the initial material is most probably: H 'f.

. and it may be priepared by reactinghexachloro- 1,2,8,7anthraquinone diacridone [with 5 benzoylamino-l-amino anthraquinone in the presenceof sodium acarbonat e and cuprous chloride.)

The resultingcondensationiproduct dissolves in n concentrated sulfuricacidwith a dull bluish-violet'color. It is readily solublein the sodium-hydrosulfite vat, from whichcotton is dyed a redbrown color changing upon oxidation to a 'yellow-, ish-brown, f' d If, in the above :examples, the corresponding 1,2,5,6-isoine1 '-s are used as initial'gnaterial, dye stuffsof analogous properties are obtained.

It will Jpe understood that manyyariations are possible incur procedure without departing from the spirit of the same. 1

The mixture is raised condensing agen't aa' polyhalogenated a-anthraquinonyl-imino derivative of an a,a-anthraquin- -one-"d iacridone'containing not less than 4 atoms "of halogen per molecule.

t re i ly so ub e in the sodium-hydrosulfite vat, from which jcot'ton.

In the claims below, it should be understood that where werclamr newtproducmrdyostufis. or articles of manufaoturawwmean-to include these bodiesnot only in substance but also in whatever state they exist when applied to material dyed,

:printed, or pigmented therewith.

- .Wexlaimr I "1 '-1 he process of producing vat dyestufis which comprises condensing by the aid of a metal halide 2. The process of producing vat dyestufls which- 'comprisessheating with a metal halide condensl-ing :agent a halogenated anthrimide-acrldone I body. or the following general formula:

wherein R stands for a radical of the anthmquinq one series, and wherein f, indicate therpositions of attachment of the CO groups.

3. Theprocess of producing vat dyestuflswhich comprises heating with a metal halide condensing agent-a halogenated anthrimide-acridone bodyoi the-following -general *tormula: r

.whereinR standstor hydroaenorianarosl-Qmtn group of the benzeneseriespandmherem 5'. dictate the positions of attaohmcnt 06 groups.

process of produoinz a flat which comprisesheating-withia metal densing-agent BZQBzdetrachloroAM-mflnn- ,quinonylalnino 13 a,?- 411M done} V 5.,The process of producing a vat, .whichrcomprise heating with a. halide conden ng 2 agent :Bzfiz-tatmehlom-iid ibenzoylamino-hanthraquinonyhmino) anthraduinonwdiaofidonex l 1 raining lclosed condensation .polyhalogenated a anthraqllhwm m ing not less than 4 atoms of halogen per molecule.

7. Ring-closed condensation products of halogenated anthrimide-acridone bodies which before condensation have the following general formula:

Ola-q i i L wherein R stands for hydrogen or an aroyl-amino group of the benzene series and wherein indicate the positions of attachment of the CO groups.

9. A ring-closed condensation product of Bz,Bztetrachloro-4,5-di-u-anthraquinonylamino-1,2,8,- I-anthraquinone-diacridone; said dyestuif being soluble in concentrated sulfuric acid with a reddish-bordeaux color and dyeing cotton from an alkaline hydrosulfite vat a blackish color, which changes to khaki upon aerationor oxidation.

10. A ring-closed condensation product of Bz,Bz-tetrachloro-4,5-di-(5 benzoylamino-l-anthraquinonylamino) -1,2,8,7 anthraquinone diacridone; said dyestuff being soluble in concentrated sulfuric acid with a dull bluish-violet color and dyeing cotton from an alkaline hydrosulfite vat a red-brown color, which changes to yellowish brown upon aeration or oxidation.

11. The process of producing a vat dyestufi which comprises condensing by the aid of aluminum chloride a halogenated anthraquinonylimino derivative of anthraquinone-diacridone having the general formula:

[01, a anthraquinone-diacridono 8O (Halogen) wherein (1, refer to the positions of the NH groups of the heterocyclic rings, (a) refers to the position of the groups (NH R) 1, R represents a radical of the anthraquinone series, :1: stands for 1 or 2, while 1 stands for a number not less than 4.

12. The process which comprises heating in an aluminum-chloride-sodium-chloride melt at a temperature of about 170 to 180 C. a compound of the general formula:

Cl2 Ch NH HN/ 0 NH NH 0 i Y wherein R stands for hydrogen or a benzoylamino group, whereby to ring close said compound, and recovering the dyestufi formed.

13. The process which comprises heating in an aluminum-chloride-sodium-chloride melt at a temperature of about 170 to 180 C. a compound of the general formula:

HN NH 0 I NH 6 NH 0 wherein R stands for hydrogen or a benzoylamino group, whereby to ring close said compound, and recovering the dyestuff formed.

IVAN GUBELMANN. ROBERT J. GOODRICH. WILLIAM DETTWYLER. 

